US11267947B2 - Method for modifying the surface properties of elastomer cellular foams - Google Patents

Method for modifying the surface properties of elastomer cellular foams Download PDF

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US11267947B2
US11267947B2 US15/326,539 US201515326539A US11267947B2 US 11267947 B2 US11267947 B2 US 11267947B2 US 201515326539 A US201515326539 A US 201515326539A US 11267947 B2 US11267947 B2 US 11267947B2
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foam
elastomer foam
cellular elastomer
compound
porous cellular
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US20170210872A1 (en
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David Edouard
Vincent Ritleng
Loïc JIERRY
Nguyet Trang Thanh CHAU DALENCON
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Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Universite de Strasbourg
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Universite Claude Bernard Lyon 1 UCBL
Universite de Strasbourg
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1669—Cellular material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B01J35/0013—
    • B01J35/004—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/036—Use of an organic, non-polymeric compound to impregnate, bind or coat a foam, e.g. fatty acid ester
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to the field of porous solid materials, more particularly cellular polymer foams. It relates to a method for modifying the surface of elastomer cellular foams, in particular foams with apparent porosity, so that they may be used as catalyst substrates.
  • the most widely used method for producing ceramic foams consists of impregnating a polymer foam, most often a polyurethane or polyester foam, cut to the desired geometry, with a suspension of ceramic particles in an aqueous or organic solvent. The excess suspension is discharged from the polymer foam through the repeated application of compression or by centrifugation, so as to keep only a fine layer of suspension on the strands of the polymer. After one or several impregnations of the polymer foam, the latter is dried so as to evacuate the solvent while preserving the mechanical integrity of the deposited layer of ceramic powder. The foam is next sintered in order to obtain an inorganic foam usable as a catalyst substrate. This fairly complex manufacturing method creates a relatively high manufacturing cost.
  • Ceramic foams One of the advantages of ceramic foams is their chemical and thermal strength. However, excellent thermal strength is not always needed. Furthermore, ceramic foams have the drawback of concealing micro-cracks and other microstructural flaws that considerably decrease their mechanical properties. Furthermore, in many cases, recovering the active metal phase (catalyst) requires many chemical treatments.
  • One aim of the present invention is to provide new catalyst substrates that are an alternative to the catalyst substrates made from metal or ceramic foams currently used in the chemical, pharmaceutical and/or cosmetic industry in environments that do not require high thermal strength; are easy to prepare, with a low manufacturing cost; and have similar or advantageous structural characteristics.
  • Another aim of the present invention is to provide new catalysts, for heterogeneous and/or supported homogenous catalysis, with a low pressure loss and having a large specific surface, while having very good chemical inertia, and which are available in all types of geometric shapes (square, planar, cylindrical, etc.) and mechanically flexible.
  • the problem is resolved by chemically modifying the surface of a known cellular material, i.e., a cellular polymer foam (in particular elastomer) with apparent porosity.
  • a known cellular material i.e., a cellular polymer foam (in particular elastomer) with apparent porosity.
  • Cellular polymer foams also called “honeycomb foams” are well known and are commercially available for many applications. When they are made up of closed cells, they have excellent mechanical strength and are used as foam wedges, packaging foam, or in mechanical construction. At the same time, these closed cells capture air and thus give the foams excellent heat insulation properties, which are used in the building sector.
  • polymer foams in particular elastomers
  • open-cell polymer foam polymer foams with apparent porosity
  • open-cell polymer foam polymer foams
  • polyurethane foams They are used as filters, in particular in aquariums.
  • these foams are not usable as a catalyst substrate due to the low adherence of the catalysts (or their precursor compounds) on the surface of this polymer.
  • the inventors have found an appropriate surface treatment that prepares the cellular polymer foams (in particular elastomers), and particularly those with apparent porosity, to receive a catalytically active phase (here called “active phase”) or active phase precursor phase deposition.
  • active phase catalytically active phase
  • active phase precursor phase deposition active phase precursor phase deposition
  • a first object of the present invention is a method for modifying a cellular polymer foam with apparent porosity, preferably made from polyurethane, comprising the following steps: supplying a porous cellular polymer foam with apparent porosity (a) placing said cellular polymer foam in contact with at least one compound (b) chosen from among compounds including at least one catechol unit, and preferably from among catecholamines, to obtain a cellular polymer foam comprising, on its surface, an intermediate phase formed from said compound including at least one catechol unit.
  • Said cellular polymer foam is advantageously a polyurethane foam.
  • the step for placing said cellular polymer foam (a) and the compound (b) in contact is done by immersing said cellular polymer foam (a) in an aqueous solution of compound (b), or by impregnating an aqueous solution of compound (b) on said cellular polymer foam (a), or by partial or complete spraying of an aqueous solution of compound (b) on said cellular polymer foam (a).
  • said cellular polymer foam (a) comprises cells with a mean size comprised between 500 ⁇ m and 5000 ⁇ m, preferably between 2000 ⁇ m and 4500 ⁇ m, and still more preferably between 2500 ⁇ m and 4500 ⁇ m; these values are chosen in order to use the foams as a catalyst substrate.
  • Compound (b) preferably includes one (preferably only one) amine function, and is advantageously chosen from among catecholamines, and is more particularly 4-(2-aminoethyl) benzene-1,2-diol (known by the name dopamine), or a derivative thereof.
  • compound (b) can be chosen from the group made up of: dopamine, noradrenaline, adrenaline, 3-methoxytyramine, 4-aminophenol, 3,4-dihydroxyphenyl-L-alanine.
  • compound (b) is not an amine, it is preferably chosen from the group of compounds including at least one catechol unit formed by: caffeic acid, hydroxyhydroquinone, catechol, pyrogallol, morin (2′,3,4′,5′7-pentahydroxyflavone), epigallocatechin, epigallocatechin gallate, catechin and its stereoisomers, tannic acid.
  • catechol unit formed by: caffeic acid, hydroxyhydroquinone, catechol, pyrogallol, morin (2′,3,4′,5′7-pentahydroxyflavone), epigallocatechin, epigallocatechin gallate, catechin and its stereoisomers, tannic acid.
  • the method according to the invention may further include a step c) for functionalizing said cellular polymer foam by depositing a phase of at least one catalytically active material or catalytically active phase precursor, said at least one material (c) being selected from the group made up of:
  • metal complexes including at least one group capable of forming covalent bonds with the coating formed from compound (b), i.e., with the catechol or indole structural element (resulting from the cyclization of the alkylamine arm of the catecholamine during step (b)), for example a trialkoxysilane group, an amine group or a thiol group, and more particularly the coordinating compounds or organometallic molecules of the transition metals;
  • organocatalysts organic molecules capable of catalyzing the reaction, called organocatalysts, including at least one group capable of forming covalent bonds with the coating formed from compound (b);
  • metal nanoparticles preferably metal nanoparticles chosen from among Ag, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Au, Ce, or those of mixed oxides associated with these elements, such as Fe2O3, NiO2, Ni2O3, CeO2, as well as from among those of other oxides, such as TiO2, ZnO, WO3, SnO2, or any possible combinations of these nanoparticles.
  • This functionalization step can be carried out after depositing compound (b) or simultaneously.
  • the functionalization step is done at a temperature comprised between 5 and 80° C., preferably between 15 and 60° C., and still more preferably between 15 and 50° C.
  • Said metal nanoparticles have a mean particle size comprised between 0.5 and 30 nm, preferably between 0.5 and 30 nm, more preferably between 0.5 and 20 nm, and still more preferably between 0.5 and 15 nm.
  • Said catalytically active phase or catalytically active phase precursor can be deposited using at least one of the following techniques: impregnation, aerosol, or droplets; chemical vapor deposition; capillary impregnation.
  • This step can be carried out after depositing compound (b) or simultaneously.
  • the cellular foam implemented in the context of the present invention assumes the form of blocks (for example, cylindrical or cubic) or plates with any shape, but the smallest outer dimension must be significantly larger than the mean size of the cells, and typically at least three times this value, preferably at least five times. As a general rule, the smallest dimension is larger than about 3 mm, preferably larger than about 10 mm, and still more preferably larger than about 20 mm.
  • Another object of the invention is a functionalized cellular polymer foam with apparent porosity, able to be obtained using the method according to the invention.
  • Still another object of the invention is the use of a cellular polymer foam with apparent porosity able to be obtained using the method according to the invention as a catalyst substrate.
  • Still another object of the invention is the use of a functionalized cellular polymer foam with apparent porosity able to be obtained using the method according to the invention as a catalyst, and more particularly as a supported homogenous and/or heterogeneous catalyst.
  • FIGS. 1 to 8 illustrate the invention.
  • FIG. 1 shows a micrograph obtained by optical microscopy of a polyurethane cellular foam with apparent porosity used in the method according to the invention, whereof the cell size is about 4.433 ⁇ 0.362 mm; window size of about 2.423 ⁇ 0.341 mm; and bridge diameter of about 0.460 ⁇ 0.047 mm.
  • the length of the white bar in the upper right indicates 5 mm.
  • FIG. 1 ( b ) shows a micrograph obtained by optical microscopy of a polyurethane cellular foam with apparent porosity used in the method according to the invention, identifying the characteristic properties of the foam (size of the cells “ ⁇ ,” pore sizes (i.e., window size) “a,” and size of the bridges “ds”).
  • FIG. 2 b shows results obtained by x-ray photoelectron spectroscopy of the O1s/C1s atomic ratio, measured on the surface of the polyurethane elastomer cellular foam of type 8FM2 by Foampartner®, unmodified and in several states of the method according to the invention
  • the increase in the proportion of oxygen atoms relative to carbon atoms between the 8FM2 control foam and the foams modified by compound (b) attests to the grafting of the PDA (compound (b)).
  • This grafting is robust in light of the lack of variation of the O1s/C1s ratio measured after 1, 2 or 3 wash steps; cf. bars A, B and C, respectively.
  • FIGS. 3 a , 3 b and 3 c show micrographs obtained by scanning electron microscopy (SEM) of the polyurethane elastomer cellular foam at different stages of the method according to the invention.
  • FIG. 3 a is a micrograph of the non-modified polyurethane foam of type C31410 BulprenTM by Recticel®. The length of the white bar in the bottom right indicates 10 ⁇ m.
  • FIG. 3 b is a micrograph of the polyurethane foam shown in FIG. 3 a after placement in contact with an aqueous dopamine solution, also called 4-(2-aminoethyl) benzene-1,2-diol (CAS: 51-61-6).
  • aqueous dopamine solution also called 4-(2-aminoethyl) benzene-1,2-diol (CAS: 51-61-6).
  • the length of the white bar in the bottom right indicates 10 ⁇ m.
  • FIG. 3 c is a micrograph of the polyurethane foam after the foam obtained in FIG. 3 b is placed in contact with an aqueous solution of TiO2 nanoparticles.
  • the length of the white bar in the bottom right indicates 1 ⁇ m.
  • AO7 Acid Orange 7
  • FIGS. 5 a and 5 b show micrographs obtained by SEM (acceleration voltage 3.0 kV) of an untouched polyurethane elastomer cellular foam ( FIG. 5 a ) and one functionalized by a dopamine deposit ( FIG. 5 b ) using the method according to the invention.
  • the length of the white bar in the upper right indicates 100 ⁇ m.
  • FIGS. 6 a and 6 b show micrographs obtained by SEM (acceleration voltage 15.0 kV) of a polyurethane elastomer cellular foam after functionalization with dopamine and deposition of a TiO2 nanopowder.
  • the length of the white bar in the upper right indicates 1 ⁇ m.
  • the dark rectangle in each figure indicates the zone in which the chemical composition has been analyzed by EDX spectroscopy (x-ray emission caused by the electron beam of the SEM apparatus):
  • FIG. 6 a shows the characteristic emission lines of the elements C, O and Ti
  • FIG. 6 b only shows the emission lines of the elements O and C.
  • FIGS. 7 and 8 relate to experiments done with a catalytic foam prepared according to example 8.
  • FIG. 8 shows the stress—deformation curve for a new specimen (curve 1) and after 5,000 compression cycles at 25% (curve 2).
  • FIG. 7 relates to a photocatalytic performance test of a catalytic foam prepared according to example 8. It corresponds to a conversion test as a function of time for a polyurethane elastomer cellular foam after functionalization with dopamine and deposition of a TiO2 nanopowder, new (curve 1) and after 5,000 compression cycles at 25% (curve 2).
  • the cellular (also called “honeycomb”) polymer foams (and in particular elastomers) used in the context of the method according to the invention are so-called solid foams with apparent porosity.
  • these are polyurethane foams.
  • the latter are commercially available in large tonnages and at low costs. They are flexible and withstand mechanical and chemical stresses particularly well, while having morphological properties allowing close mixing of the reagents, and thus the performance of chemical transformations under gentle conditions (primarily in terms of temperature and pressure) compared to systems where the catalyst is deposited on a substrate of a known type not assuming the form of an open-pore foam.
  • Honeycomb or cellular foams with apparent porosity assume the form of structures made up of interconnected cells distributed randomly throughout the entire structure of the material.
  • cellular foams have a geometry of the regular pentagonal dodecahedron type, and are classified based on their characteristic sizes ( FIG. 1 b ):
  • ⁇ mean size of the cells, corresponding to the mean equivalent diameter of the sphere fitted in the cell;
  • a mean equivalent diameter of the opening of the pores, also called size of the “windows” or size of the “pores”;
  • “ds” mean equivalent diameter of the bridges, also called characteristic length of the solid skeleton, here size of the “bridges.”
  • these foams are classified based on the number of pores (windows) per unit of length: PPI (pores per inch).
  • the modified open-cell foams according to the invention have a base of synthetic organic foam.
  • the foams according to the invention are manufactured from open-cell foams that include synthetic organic materials, preferably polyurethane foams.
  • the preparation of polyurethane cellular foams is well known by those skilled in the art.
  • such a foam may be obtained by polymerization reaction between isocyanate and alcohol.
  • the method for modifying cellular (or honeycomb) polymer foams (in particular elastomers) is a method for modifying their surface. It comprises (preferably, essentially comprises) the following two steps: in a first step, a cellular polymer foam (a) is provided, preferably a polyurethane elastomer cellular foam, with apparent porosity, in a second step, said cellular polymer foam is placed in contact with at least one compound (b) chosen from among compounds including at least one catechol unit, and preferably from among the catecholamines.
  • said foam includes cells with a mean size ⁇ comprised between 500 ⁇ m and 5,000 ⁇ m, preferably between 2,000 ⁇ m and 4,500 ⁇ m, and still more preferably between 2,500 ⁇ m and 4,500 ⁇ m.
  • the mean equivalent diameter a of the opening of the pores (windows) of the cellular polymer foam is comprised between 100 ⁇ m and 5,000 ⁇ m, preferably between 800 ⁇ m and 3,000 ⁇ m. In another embodiment, this parameter is between 1,700 ⁇ m and 4,500 ⁇ m.
  • the mean equivalent diameter ds of the bridges of the cellular polymer foam is comprised between 50 ⁇ m and 3,000 ⁇ m, preferably between 80 ⁇ m and 2,500 ⁇ m. In another embodiment, this parameter is situated between 200 ⁇ m and 2,500 ⁇ m.
  • the PPI number will be comprised between 5 PPI and 100 PPI, preferably between 30 and 75 PPI.
  • the mean cell size ⁇ is between 2,000 ⁇ m and 4,500 ⁇ m
  • the mean window size a is between 800 ⁇ m and 3,000 ⁇ m
  • the mean bridge diameter ds is between 80 ⁇ m and 2,000 ⁇ m.
  • the mean cell size ⁇ is between 2,500 ⁇ m and 4,500 ⁇ m
  • the mean window size a is between 1,000 ⁇ m and 3,000 ⁇ m
  • the mean bridge diameter ds is between 100 ⁇ m and 1,500 ⁇ m.
  • the mean cell size ⁇ is between 3,000 ⁇ m and 5,000 ⁇ m
  • the mean window size a is between 1,300 ⁇ m and 3,500 ⁇ m
  • mean bridge diameter ds is between 130 ⁇ m and 1,750 ⁇ m.
  • “Catecholamine” here refers to a compound including a catechol core (1,2-dihydroxybenzene), the benzene core further including a side chain of alkyl amine, optionally substituted. Components including a single amine function are preferred over those including several amines or a polyamine (or a component in which a catechol unit reacts with two amines), which should be avoided.
  • said compound chosen from among the catecholamines (which are preferably catechol monoamines) is advantageously dopamine [4-(2-aminoethyl) benzene-1,2-diol (CAS: 51-61-6)], or a derivative thereof.
  • compound (b) can be chosen from the group formed by: dopamine, noradrenaline, adrenaline, 3-methoxytyramine, 4-aminophenol, caffeic acid, hydroxyhydroquinone, catechol, pyrogallol, morin (2′,3,4′,5′7-pentahydroxyflavone), epigallocatechin, epigallocatechin gallate, catechin and its stereoisomers, tannic acid, and 3,4-dihydroxyphenyl-L-alanine.
  • the polymerization process according to the invention leads to a coating that is at least partially polymerized (intermediate phase) having few or no free primary amines; this is important to allow their use in catalysis.
  • the amine or ammonium surface groups are not favorable to bind metal or oxide nanoparticles. Groups are preferred of the sulfonate, alcohol or alcoholate, carboxylic acid or carboxylic, phenyl or phenolate type.
  • the inventors have found that the presence of free amine groups does not allow the functionalization of foams including the intermediate phase according to the invention with other molecules of the amine or sulfur derivative type, to further have degrees of freedom in the modification of their surface for various catalytic applications.
  • compounds of the catecholamine type are preferred over compounds including catechol units without a nitrogen function.
  • At least one compound having at least one catechol unit and preferably a compound in the catecholamine family, and still more preferably dopamine or 4-(2-aminoethyl)benzene-1,2-diol, is supplied with aqueous solution, with a quantity comprised between 0.05% to 10% by weight, preferably 0.1% to 1%.
  • the step for placing the elastomer cellular foam (a) and the compound (b) in contact can be done via several methods.
  • the contact can be done by immersion of the elastomer cellular foam (a) in an aqueous solution of compound (b); impregnating an aqueous solution of compound (b) on an elastomer cellular foam (a); or partial or complete spraying of an aqueous solution of compound (b) on the elastomer cellular foam (a).
  • the placement of the cellular polymer foam and the aqueous solution of compound (b) in contact, in particular by impregnation, immersion or spraying, is done for a period of time comprised between 1 and 48 hours, preferably 18 and 36 hours, and still more preferably between 20 and 30 hours.
  • the placement of the cellular polymer foam (a) and the compound (b) in contact is done in a temperature range from 0 to 100° C., preferably from 15 to 35° C., and particularly preferably from 20 to 30° C.
  • the cellular polymer foam (a) is placed in contact with an aqueous solution of compound (b) at a pH comprised between 5 and 10, preferably between 8 and 9.
  • a buffer solution for example a tris(hydroxymethyl)aminomethane hydrochloride buffer solution (Tris.HCl; CAS: 1185-53-1).
  • the placement of the cellular polyurethane foam (a) and the compound (b) in contact can be carried out in an aqueous solution or in a water-miscible organic water/solvent mixture.
  • the use of water as a solvent is preferred.
  • the method according to the invention comprises an additional step c) for functionalizing the catalyst substrate by depositing a phase of at least one catalytically active material (c).
  • the functionalization of the substrate is done by grafting a catalyst in the form of a metal complex, in particular a metal complex including at least one group capable of forming covalent bonds with the coating formed from compound (b), i.e., with the catechol or indole structural element (resulting from the cyclization of the alkylamine arm of the catecholamine during step (b)); said group may for example be an alkoxysilane group, a halogenosilane group (such as a chlorosilane group), an amine group or a thiol group, and the reactions performing the formation of covalent bonds can for example be condensation reactions with hydroxyl functions of the catechol structural element, reactions leading to imine formation, additions of type 1,4. or reactions of the radical type.
  • a metal complex including at least one group capable of forming covalent bonds with the coating formed from compound (b), i.e., with the catechol or indole structural element (resulting from the cyclization of the alkylamine arm of the catecholamine
  • the metal complexes (including at least one group capable of forming covalent bonds with the catechol and/or indole structural element) used in the context of the functionalization method according to the invention are chosen from among organometallic molecules or coordinating compounds, and more particularly from among those comprising at least one transition metal.
  • the functionalization of the substrate is done by grafting a catalyst in the form of an organic molecule (organocatalyst), including at least one group capable of forming covalent bonds with the coating formed from compound (b), i.e., with the catechol or indole structural element (resulting from the cyclization of the alkylamine arm of the dopamine during step (b)); said group can for example be an alkoxysilane group, a halogenosilane group (such as a chlorosilane group), an amine group or a thiol group, and the reactions performing the formation of covalent bonds can for example be condensation reactions with hydroxyl functions of the catechol structural element, reactions carrying out imine formation, additions of type 1,4. or radical-type reactions.
  • organocatalyst organic molecule
  • the grafting of an organocatalyst makes it possible to obtain a supported organocatalyst.
  • the functionalization of the substrate is done by non-covalent grafting of the catalyst in the form of metal particles, which are advantageously metal nanoparticles.
  • the grafting of the metal particles on the surface of the substrate is effective due to the presence of catechol groups.
  • the metal particles used in the context of the functionalization method according to the invention are chosen from among those of Ag, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Au, Ce, and those of mixed oxides associated with these elements, for example, Fe2O3, NiO2, Ni2O3, CeO2, as well as from among those of other oxides such as TiO2, ZnO, WO3, SnO2, and all possible combinations of these nanoparticles.
  • the metal nanoparticles used in the context of the method according to the invention have a mean particle size comprised between 0.5 and 100 nm, preferably 0.5 and 20 nm, and still more preferably between 0.5 and 15 nm.
  • the size of the catalytic nano-objects used may depend on their composition, and in particular their metal or oxide nature: the surface properties are strongly related to the size of the metal nanoparticles (gold and ruthenium, for example), less so in the case of oxides (TiO2).
  • the step for functionalizing the catalyst substrate is done by depositing the active phase using at least one of the following techniques: impregnation, aerosol, or droplets; chemical vapor deposition; capillary impregnation.
  • This functionalization step can be carried out after depositing compound (b) or at the same time.
  • the step for functionalizing the catalyst substrate is done at a temperature comprised between 5 and 80° C., preferably between 15 and 60° C., and still more preferably between 15 and 50° C.
  • the invention makes it possible to make notable improvements relative to the heterogeneous catalysts supported by rigid cellular foams, for example carbon foams, silicon carbide foams, metal foams, or alumina foams.
  • rigid cellular foams for example carbon foams, silicon carbide foams, metal foams, or alumina foams.
  • polyurethane foams which are elastomer foams, have great flexibility and better impact resistance compared to the metal or ceramic foams typically used.
  • the active phases of the cellular foams obtained using the method according to the invention can be recovered easily, for example through simple combustion of the cellular foams, which is a non-negligible advantage, in particular when the materials used as active phase are very costly.
  • recovering the active phase requires complex and polluting chemical treatments.
  • One particularity of the catalysis substrates according to the invention is related to the choice of compound (b), which is chosen from among compounds having at least one catechol unit, and preferably from among the catecholamines.
  • compound (b) which is chosen from among compounds having at least one catechol unit, and preferably from among the catecholamines.
  • the primary drawback of polymer foams for use as a catalyst substrate is their low temperature resistance: it is not possible to subject the active phase precursors (for example, metal oxides) deposited on these substrates to the same activation treatments (typically: hydrogen production) as when they are deposited on a metal or ceramic foam because this reaction requires a temperature that risks damaging the polymer foam.
  • the presence of a compound having at least one catechol unit stabilizes the chemical integrity of the nanoparticles, in particular relative to the oxidizing action of the air, which may damage or deactivate the nanoparticles.
  • the modified cellular polymer foam that may be obtained using the method according to the invention is used as a supported homogenous catalyst or as a supported organocatalyst (which is impossible with metal or ceramic foams, which may only be used as heterogeneous metal catalyst substrates)
  • the separation of the products and the catalyst is made considerably easier relative to the non-supported catalysts in particular used in fine chemistry or in hydroformylation reactions, which allows the passage to the industrial scale for reactions for which it would have been impossible to consider using them under homogenous conditions, in particular due to the difficulty of separating the homogenous catalyst from the reaction products.
  • the residual metal level (coming from a metal catalyst) in the product obtained by catalysis must not exceed a threshold set at a very low level.
  • the method according to the invention allows catalytic reactions under “gentler” temperature and pressure conditions than in a traditional reactor (discontinuous, semi-continuous or closed reactor, called “batch reactor”) owing to the material transfer properties of the foam, in particular in the case of bi-phase reactions (gas/liquid), as in hydrogenation or hydroformylation.
  • the modified cellular foams that may be obtained using the method according to the invention have many advantages relative to the rigid metal or ceramic foams currently used as catalyst substrates in the chemical, pharmaceutical and/or cosmetic industry.
  • rigid metal or ceramic foams have a certain number of limitations. In particular, they lack flexibility: the metal or ceramic foams traditionally used break very easily.
  • the choice of catalyst types that can be supported is limited to metal (nano)particles adsorbed on the surface, therefore only heterogeneous metal catalysts.
  • the catalysts deposited on these known substrates are not very durable, their aging primarily being due to the desorption and oxidation of the metal species on the foam. And lastly, rigid metal or ceramic foams are fairly expensive.
  • the cellular polymer foams modified according to the invention by placement in contact with at least one compound chosen from among the catecholamines undergo other chemical functionalization, for example covalent grafting of compounds including silane groups, amine groups or thiol groups. This makes it possible to further broaden the spectrum of surface properties that can be imparted to the cellular polymer foams using the method according to the invention.
  • Example 1 pertains to placing a polyurethane cellular foam in contact with an aqueous dopamine solution.
  • Example 2 pertains to the functionalization of the cellular foam obtained in example 1 with an aqueous fluoresceinamine solution.
  • Example 3 pertains to the functionalization of the cellular foam obtained in example 1 with a suspension in aqueous medium of titanium dioxide TiO2 nanoparticles.
  • Example 4 pertains to the functionalization of the cellular foam obtained in step 1 with a suspension in aqueous medium of ruthenium (Ru(0)) nanoparticles.
  • Example 5 pertains to the photocatalysis of acid orange 7 using the functionalized cellular foam obtained in example 3.
  • Example 6 pertains to hydrogenation tests of the styrene using the functionalized cellular foam obtained in example 4.
  • Example 7 pertains to the functionalization of a polyurethane cellular foam modified by dopamine, by the Michael 1,4-addition of a thiol or the Schiff base reaction (and/or by the Michael 1,4-addition) of an amine.
  • Example 8 pertains to a functionalization combined into one step of a polyurethane cellular foam with an aqueous dopamine solution containing titanium dioxide TiO2 nanoparticles.
  • PU-PDA Polyurethane foam comprising an intermediate polydopamine phase on its surface.
  • Pu-PDA-Fluo Polyurethane foam comprising an intermediate polydopamine phase and an upper fluoresceinamine phase.
  • PU-PDA-Ru(0) Polyurethane foam comprising an intermediate polydopamine phase and a catalytic active phase made up of ruthenium nanoparticles.
  • PU-PDA-TiO2 Polyurethane foam comprising an intermediate polydopamine phase and a catalytic active phase made up of titanium dioxide nanoparticles.
  • a polyvalent substrate for heterogeneous catalysts or supported homogenous catalysts was obtained by placing a polyurethane elastomer cellular foam in contact with a dopamine solution, this method corresponding to reaction diagram 1 below:
  • the reaction mixture is agitated at ambient temperature for 24 hours.
  • the dopamine to polydopamine polymerization process is characterized by the change of color of the reaction medium to dark brown.
  • the polyurethane foam grafted with the polydopamine (PU-PDA) is next rinsed with ultrapure water (MiliQ), then agitated in 50 mL of MiliQ water for 10 min. The washing procedure is repeated 5 times.
  • the persistent brownish color on the surface of the foam is characteristic of the effective grafting of the PDA.
  • the obtained product is dried by compressed air flow, then in a drying oven (60-70° C.) for one night.
  • the PU-PDA foam obtained in example 1 was functionalized with an aqueous fluoresceinamine solution to form a fluorescent compound called PU-PDA-Fluo.
  • the purpose of this example is in particular to demonstrate that it is possible to functionalize the polydopamine by reaction with an amine group (by Schiff base reaction and/or Michael 1,4-addition), which makes it possible to consider PU-PDA functionalization with any molecule including an amine group, including metal complexes.
  • This fluorescent compound in fact allows easy viewing of the functionalization of the polydopamine layer formed on the surface of the polyurethane foam using optical fluorescence microscopy techniques.
  • the PU-PDA foam prepared according to example 1 is submerged in an agitated solution of 5-aminofluorescein (CAS: 3326-34-9, also called fluoresceinamine, isomer I), prepared by dilution of 5-aminofluorescein (0.5 mg/mL) in an aqueous solution of Tris.HCl at 10 mM (pH 8.5, 60 mL) prepared according to example 1.
  • the reaction mixture is agitated and heated at 60° C. for 3 hours, then agitated at ambient temperature for 16 hours.
  • the PU-PDA foam grafted with the fluoresceinamine (PU-PDA-fluoresceinamine) is next rinsed with ultrapure water (MiliQ), then agitated in 50 mL of MiliQ water for 10 min. The washing procedure is repeated 3 times.
  • the PU-PDA-Fluo foam thus obtained is dried by compressed air flow, then is kept at ambient temperature.
  • the fluorescence microscopy analysis (excitation at 365 nm) confirms the presence of fluoresceinamine on the PU-PDA-Fluo foam surface; the layer is continuous and homogenous.
  • the fluorescence intensity (measured using the ImageJ® software) on a given surface is twice as high when the PU-PDA foam is modified by fluoresceinamine, relative to the same foam not modified.
  • the PU-PDA foam obtained in example 1 was functionalized with a suspension in aqueous medium of titanium dioxide metal nanoparticles to form a catalyst called PU-PDA-TiO2.
  • the PU-PDA foam grafted with the TiO2 nanoparticles (PU-PDA-TiO2) is next rinsed with MiliQ ultrapure water, then agitated in 50 mL of MiliQ water for 10 min. The washing procedure is repeated 5 times.
  • the obtained product (PU-PDA-TiO2) is dried by compressed air flow, then in the drying oven (60-70° C.) for one night.
  • the PU-PDA foam obtained in example 1 was functionalized with a suspension in aqueous medium of metal ruthenium nanoparticles to form a catalyst called PU-PDA-Ru(0).
  • the reaction diagram for the preparation of this foam is shown below:
  • aqueous solution 50 mL
  • RuCl3.3H2O 26.1 mg; 0.1 mM
  • NaBh4 a freshly prepared aqueous solution
  • the reduction process occurs quickly and is characterized by the gradual change of color; from dark brown to light brown, then green-brown, and lastly back to dark brown.
  • the addition of NaBH4 is complete when the reaction medium has become dark brown again (pH ⁇ 4.9).
  • the colloidal solution is next agitated for one night at ambient temperature to obtain a well-dispersed suspension of ruthenium(0) nanoparticles, with a particle size comprised between 1 and 2 nm.
  • the PU-PDA foam prepared according to example 1 is submerged in this ruthenium nanoparticle suspension, then the reaction medium is agitated at ambient temperature for 24 hours.
  • the PU-PDA foam grafted with the ruthenium(0) nanoparticles (PU-PDA-Ru(0)) is next rinsed with MiliQ water, then agitated in 50 mL of MiliQ water for 10 min. The washing procedure is repeated 5 times.
  • the PU-PDA-Ru(0) is dried by compressed air flow, then in the drying oven (60-70° C.) for one night.
  • this reaction can form as a secondary product of the ethylcyclohexane 3.
  • the hydrogenation of the styrene 1 is done in a glass 4-neck reactor (250 mL) equipped with a condenser.
  • the PU-PDA-Ru(0) is fixed at the end of the mechanical agitator in a glass cage with holes.
  • the catalyst is submerged in a styrene solution (0.23 mL; 0.02 M) in ethanol (100 mL).
  • the reaction medium is heated at 70° under mechanical agitation (about 450 revolutions/minute) and the hydrogen is boiled continuously in the solution with the flow rate of 60 mL/min. After 6 and 22 hours of reaction, 0.5 mL of the reaction medium is withdrawn and analyzed by gas chromatography to determine the conversion.
  • HS—(CH2)2-COOH was grafted on a C31410 BulprenTM polyurethane foam by the company Recticel® modified with polydopamine (PU-PDA) via the Michael 1,4-addition of the thiol function on the aromatic cycle of the PDA.
  • PU-PDA polydopamine
  • HS—(CH2)2-COOH was used at a rate of 0.5 mg/mL in an aqueous solution of NaOH (0.1 M) at ambient temperature.
  • the presence of the thiol on the PU-PDA foam thus modified was demonstrated by XPS.
  • NH2-(CH2)6-NH2 was grafted on a C31410 BulprenTM polyurethane foam by the company Recticel® modified with polydopamine (PU-PDA) via a Schiff base reaction (and/or a Michael 1,4 reaction).
  • PU-PDA polydopamine
  • NH2-(CH2)6-NH2 was used under the following conditions: at a rate of 0.5 mg/mL in an aqueous Tris solution (15 mM) with a pH of 8.6 at 60° C. for three hours, followed by 16 hours at a.t.
  • the presence of the amine on the PU-PDA foam thus modified was demonstrated by XPS.
  • a PU-PDA-TiO2 catalyst was obtained in a single step by placing a polyurethane elastomer cellular foam in contact with a suspension of titanium oxide metal nanoparticles in a dopamine aqueous solution.
  • a polyurethane foam specimen similar to that used in example 1 is submerged, then the reaction mixture is agitated at about 1,000 revolutions/minute and heated at 40° C. for 24 hours.
  • the PU-PDA foam grafted with the TiO2 nanoparticles (PU-PDA-TiO2) is next rinsed with MiliQ ultrapure water, then agitated in 50 mL of MiliQ water for 10 min. The washing procedure is repeated 5 times.
  • the obtained product (PU-PDA-TiO2) is dried by compressed air flow, then in the drying oven (60-70° C.) for at least 12 hours.

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